Supporting information 1 · 2013-04-30 · 1 Supporting Information 1 A new MCM-41 supported HPF 6...
Transcript of Supporting information 1 · 2013-04-30 · 1 Supporting Information 1 A new MCM-41 supported HPF 6...
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Supporting Information 1
A new MCM-41 supported HPF6 catalyst for the library synthesis of highly substituted 1,4-dihydropyridines and oxidation to pyridines:
report of one-dimensional packing towards LMSOMs and studies on their photophysical properties
Suman Raya, Mike Brownb, Asim Bhaumikc, Arghya Duttac and Chhanda Mukhopadhyaya*
a: Department of Chemistry, University of Calcutta, 92 APC Road, Kolkata-700009, India b: Bruker Bio Spin, 2700 Technology Forest Drive, Woodlands, Texas 77381, USA
c: Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India.
Table of Contents
Materials and Methods ………………………………….…………….….…......... 2
ORTEP DIAGRAM for 5d, 6i, 6r……….................................................................3
General synthetic procedure for the preparation of 5a-5w…………………….….4
Spectroscopic characterization for 5a-5w……………………………………....5-15
1H NMR and 13C NMR spectra for 5a-5w…….................................................16-36
Preparation MCM-41 supported HPF6 catalyst………………………………........37
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Materials and Methods
All solvents were dried by standard methods. Chemicals were purchased from Aldrich, USA and Spectrochem, India
and used without further purification. TLC was done on glass sheets pre-coated with silica gel (with binder, 300
mesh, Spectrochem). The 1H- and 13C-NMR analysis were carried out on Bruker-Advance Digital 300 MHz and
75.5 MHz instruments in D6-DMSO and CDCl3 with TMS as an internal reference. The chemical shifts were
reported as δ values (ppm) relative to TMS. IR spectra were recorded in KBr pellets in reflection mode on a Perkin
Elmer RX-1 FTIR spectrophotometer. CHN analysis was performed using a Perkin-Elmer 2400 Series II CHN
analyzer. X-ray diffraction patterns of the powder sample were obtained with a Seifert P3000 diffractometer using
Cu Kα (λ = 0.15406 nm) radiation. Nitrogen adsorption/desorption isotherms were obtained using a Quantachrome
Autosorb 1C at 77 K. Prior to gas adsorption, all the samples were degassed for 2 h at 403 K. Transmission electron
microscopic images were recorded on a JEOL 2010 TEM operated at 200 kV in Indian Association for the
Cultivation of Science, Jadavpur, Kolkata 700 032, India. The 29Si MAS NMR was referenced with respect to
external TMS using 7mm zirconia rotor and 2.5–3.5 kHz speed for more than 5 h, scanning around 5000 scans in
NMR Research Centre, IISc, Bangalore-560012.
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Fig
Figu
Figu
gure 1. Ortep diag
ure 2. Ortep diagra
re 3. Ortep diagram
ram of 5d showing
am of of (6i) showi
m of of (6r) show
3
g the crystallograp
ing the crystallogr
ing the crystallogr
phic numbering (C
raphic numbering (
raphic numbering
CCDC 853740).
(CCDC 884043).
(CCDC 853739).
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General synthetic procedure for the preparation of 5a-5w
All the reactions were carried out in a round bottom flask equipped with a magnetic stirrer. In a typical reaction a
solution of ketone (1 mmol), 1,3-diketoneone (1 mmol), aldehyde (1 mmol), and ammonium carbonate (1.2 mmol)
in water (2 ml) were stirred at room temperature till completion using 40 mg of silica-HPF6 catalyst. The completion
of the reaction was indicated by the disappearance of the starting material in thin layer chromatography. After
completion of the reaction the crude product was taken in dichloromethane and filtered to separate the products as
filtrate from the catalyst (residue). The solvent was evaporated in rotary evaporator and the crude product was
further purified by silica gel column chromatography (25% ethyl acetate/75% petroleum ether). The products were
characterized by IR, 1H NMR, 13NMR, CHN and X-ray single crystal analysis. The spectral and analytical data of all
the novel 1,4-dihydropyridine compounds are given below.
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Spectroscopic characterization for 5a-5w:
N
O
H
Cl
4-(4-chlorophenyl)-7,8-dihydro-7,7-dimethyl-2,3-diphenylquinolin-5(1H,4H,6H)-one (5a):
Yellow solid, mp 240-242 °C; IR νmax (KBr) 3435, 3012, 2962, 1685, 1573, 1518, 1457, and 1238 cm-1; 1H NMR
(300 MHz, CDCl3) δ: 7.27 (2H, d, J = 8.1 Hz), 7.17-7.11 (7H, m), 6.93 (3H, brs), 6.78 (2H, d, J = 3.6 Hz), 5.99 (1H,
s), 4.90 (1H, s), 2.42-2.06 (4H, m), 1.03 (3H, s), 0.83 (3H, s); 13C NMR (75 MHz, CDCl3) δ: 195.1, 149.4, 144.8,
139.4, 136.4, 132.7, 131.6, 129.8, 129.6, 129.2, 129.0, 128.7, 128.5, 127.7, 127.6, 126.2, 118.2, 116.4, 50.7, 41.7,
41.5, 32.6, 29.8, 26.7; Anal. Calcd for C29H26ClNO: C, 79.17; H, 5.96; N, 3.18. Found C, 79.34; H, 6.00; N, 3.26.
N
O
H
Br
4-(4-bromophenyl)-7,8-dihydro-7,7-dimethyl-2,3-diphenylquinolin-5(1H,4H,6H)-one (5b):
Yellow solid, mp 280-282 °C; IR νmax (KBr) 3434, 3011, 2968, 1681, 1573, 1510, 1458, and 1238 cm-1; 1H NMR
(300 MHz, CDCl3) δ: 7.30-7.15 (9H, m), 6.94-6.01 (3H, m), 6.80-6.74 (2H, m), 4.89 (1H, s), 2.53-2.11 (4H, m),
1.04 (3H, s), 0.84 (3H, s); 13C NMR (75 MHz, CDCl3) δ: 193.0, 150.1, 145.6, 139.4, 135.2, 133.6, 130.4, 130.0,
129.8, 129.2, 129.0, 128.6, 127.6, 127.0, 126.8, 125.2, 118.2, 113.1, 106.0, 49.8, 40.9, 31.3, 29.0, 25.4; Anal. Calcd
for C29H26BrNO: C, 71.90; H, 5.41; N, 2.89. Found C, 71.61; H, 5.43; N, 2.60.
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N
O
H
NO2
7,8-dihydro-7,7-dimethyl-4-(3-nitrophenyl)-2,3-diphenylquinolin-5(1H,4H,6H)-one (5c):
Yellow solid, mp 206-208 °C; IR νmax (KBr) 3434, 3050, 2970, 1685, 1573, 1518, 1457, and 1244 cm-1; 1H NMR
(300 MHz, CDCl3) δ: 8.28 (1H, d, J = 1.8 Hz), 7.99 (1H, dd, J = 7.2 Hz and J = 1.2 Hz), 7.34 (1H, t, J = 7.8 Hz),
7.27 (5H, brs), 7.02-7.00 (3H, m), 6.86-6.83 (2H, m, aromatic-H), 5.99 (1H, s), 5.17 (1H, s), 2.51-2.16 (4H, m), 1.12
(3H, s), 0.92 (3H, s); 13C NMR (75 MHz, CDCl3) δ: 194.5, 153.7, 150.1, 146.3, 139.0, 136.1, 134.6,129.5, 129.0,
128.7, 128.6, 127.9, 126.5, 122.5, 121.3, 115.9, 108.1, 50.6, 42.8, 41.5, 32.6, 29.7, 26.7; Anal. Calcd for
C29H26N2O3: C, 77.31; H, 5.82; N, 6.22. Found C, 77.31; H, 5.90; N, 6.41.
N
O
H
NO2
7,8-dihydro-7,7-dimethyl-4-(4-nitrophenyl)-2,3-diphenylquinolin-5(1H,4H,6H)-one (5d) (Table 1, entry
1):yellow solid, mp 254-256 °C; IR νmax (KBr) 3434, 3012, 2949, 1685, 1573, 1518, 1457, and 1244 cm-1; 1H NMR
(300 MHz, CDCl3) δ: 8.10 (2H, d, J = 8.4 Hz), 7.56 (2H, d, J = 8.4 Hz), 7.26 (5H, d, J = 2.4 Hz), 7.02-7.00 (3H, m),
6.84-6.81 (2H, m), 6.16 (1H, brs), 5.14 (1H, s), 2.53-2.04 (4H, m), 1.12 (3H, s), 0.91 (3H, s); 13C NMR (75 MHz,
CDCl3) δ: 194.9, 153.5, 150.1, 146.3, 139.0, 136.0, 133.3,129.4, 128.9, 128.7, 127.8, 126.5, 123.6, 122.7, 115.9,
108.1, 50.6, 42.8, 41.5, 32.6, 29.7, 26.7; Anal. Calcd for C29H26N2O3: C, 77.31; H, 5.82; N, 6.22. Found C, 77.60; H,
5.92; N, 6.02.
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N
O
H
CN
4-(7,7-Dimethyl-5-oxo-2,3-diphenyl-1,4,5,6,7,8-hexahydro-quinolin-4-yl)-benzonitrile (5e):
Yellow solid, mp 288-290 °C; IR νmax (KBr) 3432, 3018, 2960, 1685, 1561, 1518, 1451, and 1245 cm-1; 1H NMR
(300 MHz, DMSO-D6) δ: 9.04 (1H, s), 7.68 (2H, d, J = 7.8 Hz), 7.42 (2H, d, J = 8.4 Hz), 7.24 (5H, br s), 6.95-6.94
(3H, m), 6.73-6.70 (2H, m), 4.86 (1H, s), 2.51-1.91 (4H, m), 0.98 (3H, s), 0.73 (3H, s); 13C NMR (75 MHz, DMSO-
D6) δ: 193.6, 152.2, 151.3, 139.8, 135.7, 134.6, 132.3, 129.7, 129.2, 128.5, 128.3, 127.8, 126.0, 119.1, 113.4, 108.7,
106.1, 50.4, 42.6, 32.0, 29.6, 26.1; Anal. Calcd for C30H26N2O: C, 83.69; H, 6.09; N, 6.51. Found C, 83.95; H, 6.17;
N, 6.56.
N
CH3
O
H
NO2
3,7,7-Trimethyl-4-(3-nitro-phenyl)-2-phenyl-4,6,7,8-tetrahydro-1H-quinolin-5-one (5f):
Wellowish white solid, mp 250-252 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3432, 3061, 2972, 1684,
1572, 1518, 1458, and 1241 cm-1; 1H NMR (300 MHz, CDCl3) δ: 8.23 (1H, s), 8.02 (2H, dd, J = 8.1 Hz and J = 1.2
Hz), 7.77 (2H, d, J = 7.5 Hz), 7.45-7.33 (6H, m), 6.22 (1H, br s), 4.64 (1H, s), 2.43-1.99 (4H, m), 1.52 (3H, s), 1.08
(3H, s), 0.93 (3H, s); 13C NMR (75 MHz, DMSO-D6) δ: 192.8, 151.0, 148.7, 147.2, 134.9, 133.7, 130.8, 128.9,
128.6, 127.8, 127.7, 127.5, 121.3, 120.4, 109.4, 104.249.6, 42.3, 31.3, 28.8, 27.3, 25.7, 16.7; Anal. Calcd for
C24H24N2O3: C, 74.21; H, 6.23; N, 7.40. Found C, 74.51; H, 6.30; N, 7.40.
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N
CH3
O
H
Br
4-(4-Bromo-phenyl)-3,7,7-trimethyl-2-phenyl-4,6,7,8-tetrahydro-1H-quinolin-5-one (5g):
Yellowish white solid, mp 140-142 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3438, 3010, 2961, 1688,
1574, 1512, 1458, and 1231 cm-1; 1H NMR (300 MHz, CDCl3) δ: 7.37-7.20 (9H, m), 6.03 (1H, br s), 4.40 (1H, s),
2.34-1.91 (4H, m), 1.46 (3H, s), 1.01 (3H, s), 0.93 (3H, s); 13C NMR (75 MHz, CDCl3) δ: 196.8, 160.8, 158.8, 148.8,
139.2, 138.2, 131.9, 130.5, 130.2, 129.8, 129.1, 128.8, 128.6, 128.5, 127.9, 127.7, 127.5, 127.4, 122.9, 119.6, 52.5,
45.8, 31.7, 27.2, 16.7; Anal. Calcd for C24H24BrNO: C, 68.25; H, 5.73; N, 3.32. Found C, 68.20; H, 5.77; Br, N,
3.32.
N
CH3
O
H
NO2
7,8-dihydro-3,7,7-trimethyl-4-(4-nitrophenyl)-2-phenylquinolin-5(1H,4H,6H)-one (5h):
Yellow solid, mp 244-246 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3430, 3068, 2951, 2869, 1681, 1576,
1530, and 1347 cm-1; 1H NMR (300 MHz, DMSO-D6) δ: 8.74 (1H, s), 8.16 (2H, dd, J = 6.9 Hz and J = 1.8 Hz),
7.57 (2H, dd, J = 6.9 Hz and J = 1.8 Hz), 7.47-7.32 (7H, m), 4.53 (1H, s), 2.51-1.90 (4H, m), 1.40 (3H, s), 1.00 (3H,
s), 0.85 (3H, s); 13C NMR (75 MHz, DMSO-D6) δ: 192.7, 154.2, 150.9, 145.2, 134.9, 130.7, 128.6, 128.2, 127.8,
127.7, 123.1, 122.7, 109.2, 104.1, 49.6, 42.7, 31.3, 28.8, 25.9, 16.8; Anal. Calcd for C24H24N2O3: C, 74.21; H, 6.23;
N, 7.40. Found C, 74.44; H, 6.30; N, 7.21.
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N
CH3
O
H
CN
4-(1,4,5,6,7,8-hexahydro-3,7,7-trimethyl-5-oxo-2-phenylquinolin-4-yl)benzonitrile (5i):
Yellowish white solid, mp 244-250 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3434, 3067, 2951, 2869,
1681, 1576, 1530, 1349, and 1245 cm-1; 1H NMR (300 MHz, DMSO-D6) δ: 8.70 (1H, s), 7.74 (2H, dd, J = 6.6 Hz
and J = 1.8 Hz), 7.50-7.31 (7H, m), 4.45 (1H, s), 2.49-1.86 (4H, m), 1.39 (3H, s), 1.06 (3H, s), 0.84 (3H, s); 13C
NMR (75 MHz, DMSO-D6) δ: 192.7,152.0, 151.0, 134.9, 131.4, 130.7, 128.6, 128.5, 128.0, 127.8, 127.7, 127.5,
118.5, 109.3, 108.0, 104.1, 49.7, 42.8, 31.3, 28.8, 25.9, 16.9; Anal. Calcd for C25H24N2O: C, 81.49; H, 6.57; N, 7.60.
Found C, 81.88; H, 6.66; N, 7.62.
N
CH3
O
H
OMe
7,8-dihydro-4-(4-methoxyphenyl)-3,7,7-trimethyl-2-phenylquinolin-5(1H,4H,6H)-one (5j):
Yellowish white solid, mp 194-196 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3434, 3067, 2951, 2869,
1681, 1576, 1530, and 1349 cm-1; 1H NMR (300 MHz, CDCl3) δ: 7.52-7.20 (9H, m), 6.15 (1H, s), 4.45 (1H, s),
2.45-1.94 (4H, m), 1.53 (3H, s), 1.05 (3H, s), 0.94 (3H, s); Anal. Calcd for C25H27NO2: C, 80.40; H, 7.29; N, 3.75.
Found C, 80.10; H, 7.38; N, 3.71.
N
CH3
O
H
Cl
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4-(4-chlorophenyl)-7,8-dihydro-3,7,7-trimethyl-2-phenylquinolin-5(1H,4H,6H)-one (5k):
Yellowish white solid, mp 200-202 °C; IR νmax (KBr) 3434, 3059, 2959, 2869, 1681, 1576, 1526, and 1344 cm-1; 1H
NMR (300 MHz, CDCl3) δ: 7.40-7.29 (7H, m), 7.80 (2H, d, J = 7.8 Hz), 6.25 (1H, s), 4.42 (1H, s), 3.75 (3H, s),
2.36-1.98 (4H, m), 1.54 (3H, s), 1.09 (3H, s), 0.92 (3H, s); Anal. Calcd for C24H24ClNO: C, 76.28; H, 6.40; N, 3.71.
Found C, 76.28; H, 6.49; N, 3.58.
N
HO
HCl
NO2
2-(4-Chloro-phenyl)-3,7,7-trimethyl-4-(3-nitro-phenyl)-4,6,7,8-tetrahydro-1H-quinolin-5-one (5l):
Yellow solid, mp 268-270 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3170, 3074, 1666, 1588, 1531, 1499,
1388, and 1349 cm-1; 1H NMR (300 MHz, DMSO-D6) δ: 8.77 (1H, s), 8.00-7.95 (2H, m), 7.67 (1H, d, J = 7.8 Hz),
7.56-7.41 (5H, m), 5.25 (1H, d, J = 5.1 Hz), 4.72 (1H, d, J = 5.1 Hz), 2.19-1.95 (4H, m), 1.00 (3H, s), 0.92 (3H, s);
13C NMR (75 MHz, DMSO-D6) δ: 194.0, 153.0, 150.3, 147.9, 134.4, 134.3, 133.7, 133.1, 129.7, 128.5, 127.6,
121.8, 120.9, 105.3, 50.3, 37.3, 32.0, 29.2, 26.8; Anal. Calcd for C23H21ClN2O3: C, 67.56; H, 5.18; N, 6.85. Found
C, 67.86; H, 5.20; N, 7.00.
N
HO
HNO2
NO2
7,8-dihydro-7,7-dimethyl-4-(3-nitrophenyl)-2-(4-nitrophenyl)quinolin-5(1H,4H,6H)-one (5m):
Yellow solid, mp 294-296 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3188, 3074, 2964, 1661, 1589, 1531,
1499, 1388, and 1345 cm-1; 1H NMR (300 MHz, DMSO-D6) δ: 9.90 (1H, s), 8.64 (2H, d, J = 8.7 Hz), 8.45-8.33 (3H,
m), 8.19 (2H, d, J = 9.0 Hz), 8.12 (1H, d, J = 7.5 Hz), 8.03-7.98 (2H, m), 5.92 (1H, d, J = 4.2 Hz), 5.20 (1H, d, J =
5.1 Hz), 2.65-2.37 (4H, m), 1.45 (3H, s), 1.37 (3H, s); 13C NMR (75 MHz, DMSO-D6) δ: 193.5, 152.4, 149.5, 149.2,
148.6, 147.2, 146.8, 146.6, 140.3, 133.9, 133.7, 133.4, 133.2, 129.2, 1218.6, 128.1, 126.2, 123.1, 121.4, 121.2,
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120.4, 120.1, 110.0, 107.6, 104.6, 49.6, 36.8, 33.0, 31.6, 28.5, 28.4, 27.2, 26.2; Anal. Calcd for C23H21N3O5: C,
65.86; H, 5.05; N, 10.02. Found C, 66.06; H, 5.15; N, 10.00.
N
HO
H
S
7,8-dihydro-7,7-dimethyl-4-phenyl-2-(thiophen-2-yl)quinolin-5(1H,4H,6H)-one (5n): yellowish white solid, mp
194-196 °C; IR νmax (KBr) 3432, 3067, 2951, 2859, 1686, 1576, 1526, and 1344 cm-1; 1H NMR (300 MHz, CDCl3)
δ: 7.32 (2H, d, J = 7.5 Hz), 7.24 (2H, t, J = 7.5 Hz), 7.19-7.10 (2H, m), 7.07 (1H, d, J = 2.4 Hz), 6.96 (1H, t, J = 3.6
Hz), 6.22 (1H, brs), 5.35(1H, d, J = 5.1 Hz), 4.68 (1H, d, J = 5.1 Hz), 2.38-2.10 (4H, m), 1.06 (3H, s), 0.98 (3H, s);
Anal. Calcd for C22H23NOS: C, 75.61; H, 6.63; N, 4.01. Found C, 75.90; H, 6.70; N, 4.21.
N
HO
H
S
OMe
7,8-dihydro-4-(4-methoxyphenyl)-7,7-dimethyl-2-(thiophen-2-yl)quinolin-5(1H,4H,6H)-one (5o):
Yellowish white solid, mp 212-214 °C; IR νmax (KBr) 3432, 3067, 2951, 2869, 1681, 1576, 1530, and 1344 cm-1; 1H
NMR (300 MHz, CDCl3) δ: 7.26 (2H, d, J = 8.7 Hz), 7.20 (1H, d, J = 5.1 Hz), 7.06 (1H, d, J = 5.4, Hz), 6.99 (1H, t,
J = 4.2 Hz), 6.80 (2H, d, J = 8.7 Hz), 6.07 (1H, s), 5.36-5.34 (1H, m), 4.64 (1H, d, J = 5.1 Hz), 3.77 (3H, s), 2.38-
2.12 (4H, m), 1.07 (3H, s), 0.99 (3H, s); Anal. Calcd for C22H23NO2S: C, 72.30; H, 6.34; N, 3.83; O. Found CC,
72.30; H, 6.34; N, 3.83; O.
N
HO
H
S
OMeOMe
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7,8-dihydro-4-(3,4-dimethoxyphenyl)-7,7-dimethyl-2-(thiophen-2-yl)quinolin-5(1H,4H,6H)-one (5p):
Yellowish white solid, mp 222-224 °C; IR νmax (KBr) 3438, 3057, 2951, 2869, 1681, 1579, 1530, and 1346 cm-1; 1H
NMR (300 MHz, CDCl3) δ: 7.20 (1H, d, J = 5.1 Hz), 7.10 (1H, d, J = 3.3, Hz), 6.98 (1H, t, J = 4.5 Hz), 6.86 (1H, d,
J = 8.1 Hz), 6.77 (1H, d, J = 8.4 Hz), 6.19 (1H, s), 5.38-5.36 (1H, m), 4.65 (1H, d, J = 5.4 Hz), 3.80 (3H, s), 3.76
(3H, s), 2.40-2.04 (4H, m), 1.08 (3H, s), 1.01 (3H, s) ; Anal. Calcd for C23H25NO3S: C, 69.84; H, 6.37; N, 3.54.
Found C, 70.03; H, 6.47; N, 3.54.
N
HO
HOMe
NO2
7,8-dihydro-2-(4-methoxyphenyl)-7,7-dimethyl-4-(3-nitrophenyl)quinolin-5(1H,4H,6H)-one (5q):
Yellow solid, mp 184-186 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3180, 3074, 2964, 1661, 1589, 1531,
1499, 1388, and 1345 cm-1; 1H NMR (300 MHz, DMSO-D6) δ: 8.69 (1H, s), 8.00-7.93 (2H, m), 7.67 (1H, d, J = 7.5
Hz), 7.58-7.48 (1H, m), 7.39 (2H, d, J = 8.7 Hz), 6.91 (2H, d, J = 9.0 Hz), 5.11 (1H, d, J = 6.6 Hz), 4.70 (1H, d, J =
5.4 Hz), 3.72 (3H, s), 2.19-1.93 (4H, m), 1.00 (3H, s), 0.95 (3H, s); 13C NMR (75 MHz, DMSO-D6) δ: 193.9, 159.6,
155.0, 150.7, 147.8, 135.1, 134.2, 129.6, 127.3, 127.1, 122.5, 121.8, 120.7, 120.4, 113.9, 111.9, 105.4, 103.3, 55.3,
50.3, 37.3, 31.7, 29.2, 28.0, 26.8; Anal. Calcd for C24H24N2O4: C, 71.27; H, 5.98; N, 6.93. Found C, 71.51; H, 5.88;
N, 6.90.
N
HO
HOMe
NO2
7,8-dihydro-2-(4-methoxyphenyl)-7,7-dimethyl-4-(4-nitrophenyl)quinolin-5(1H,4H,6H)-one (5r):
Yellow solid, mp 194-196 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3431, 3069, 2951, 2869, 1681, 1576,
1530, and 1333 cm-1; 1H NMR (300 MHz, DMSO-D6) δ: 8.34 (1H, s), 8.13 (2H, d, J = 8.4 Hz), 7.50-7.41 (4H, m),
6.95 (2H, d, J = 8.7 Hz), 5.10 (1H, d, J = 4.5 Hz), 4.72 (1H, d, J = 5.4 Hz), 3.77 (3H, s), 2.21-1.98 (4H, m), 1.04
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(3H, s), 0.95 (3H, s); 13C NMR (75 MHz, DMSO-D6) δ: 193.2, 158.9, 155.4, 152.4, 145.0, 134.4, 128.9, 128.4,
127.9, 126.7, 126.4, 122.9, 122.3, 113.7, 113.2, 104.5, 102.4, 54.7, 49.7, 37.1, 31.3, 28.5, 27.2, 26.4; Anal. Calcd for
C24H24N2O4: C, 71.27; H, 5.98; N, 6.93. Found C, 71.57; H, 5.91; N, 6.71.
N
HO
H
Br
4-(4-Bromo-phenyl)-3,7,7-trimethyl-2-phenyl-4,6,7,8-tetrahydro-1H-quinolin-5-one (5s):
Yellow solid, mp 164-166 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) ) 3434, 3067, 2951, 2869, 1681,
1577, 1525, and 1335 cm-1; 1H NMR (300 MHz, CDCl3) δ: 7.38-7.36 (7H, m), 7.25-7.22 (2H, m), 5.96 (1H, br s),
5.23 (1H, d, J = 4.8 Hz), 4.70 (1H, d, J = 5.1 Hz), 2.42-2.04 (4H, m), 1.00 (3H, s), 0.91 (3H, s); 13C NMR (75 MHz,
CDCl3) δ: 195.4, 162.3, 150.7, 146.6, 135.6, 134.4, 131.3, 129.7, 128.9, 125.1, 119.8, 108.1, 106.4, 50.7, 42.1, 37.3,
32.5, 29.4, 27.4; Anal. Calcd for C24H24BrNO: C, 68.25; H, 5.73; N, 3.32. Found C, 68.25; H, 5.73; N, 3.32.
N
HO
H
NO2
2-(9H-fluoren-2-yl)-7,8-dihydro-7,7-dimethyl-4-(3-nitrophenyl)quinolin-5(1H,4H,6H)-one (5t):
Yellow solid, mp 194-196 °C; IR νmax (KBr) 3433, 3067, 2951, 2869, 1681, 1577, 1525, and 1344 cm-1; 1H NMR
(300 MHz, CDCl3) δ: 8.21 (1H, s), 8.00 (1H, dd, J = 8.1 Hz and J = 1.2 Hz), 7.80-7.73 (3H, m), 7.59-7.54 (2H, m),
7.45-7.30 (4H, m), 6.06 (1H, s), 5.29-5.26(1H, m), 5.14 (1H, d, J = 5.1 Hz), 3.90 (2H, s), 2.55-2.15 (4H, m), 1.12
(3H, s), 1.04 (3H, s); 13C NMR (75 MHz, CDCl3) δ: 194.5, 149.7, 148.7, 144.0, 143.4, 142.7, 140.8, 135.4, 134.2,
133.7, 129.0, 127.3, 127.0, 125.1, 124.0, 122.8, 122.0, 121.2, 120.2, 107.2, 105.4, 50.6, 42.1, 38.0, 36.9, 32.6, 29.3,
27.4; Anal. Calcd for C14H16N2O3S: C, 57.52; H, 5.52; N, 9.58. Found C, 57.70; H, 5.60; N, 9.70.
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N
O
H
NO2
3,3-Dimethyl-9-(3-nitro-phenyl)-3,4,5,6,7,8,9,10-octahydro-2H-acridin-1-one (5u):
Brown liquid, IR νmax (Neat) 3434, 3067, 2951, 2869, 1681, 1576, 1530, and 1349 cm-1; 1H NMR (300 MHz,
DMSO-D6) δ: 8.34 (1H, s), 7.96-7.93 (2H, m), 7.60 (2H, d, J = 7.5 Hz), 7.49 (1H, t, J = 7.8 Hz), 4.30 (1H, s), 2.37-
2.21 (2H, m), 2.10-2.05 (3H, m), 1.90-1.85 (1H, m), 1.79-1.74 (1H, m), 1.63 (2H, br s), 1.44 (3H, br s), 0.97 (3H, s),
0.84 (3H, s); 13C NMR (75 MHz, DMSO-D6) δ: 193.2, 151.4, 149.8, 147.7, 134.3, 129.3, 128.3, 121.8, 120.7, 110.4,
105.1, 50.2, 42.3, 32.0, 29.2, 26.7, 25.6, 22.4, 22.0; Anal. Calcd for C21H24N2O3: C, 71.57; H, 6.86; N, 7.95. Found
C, 71.70; H, 6.86; N, 7.90.
N
CH3
O
HH
H
NO2
7,8-dihydro-3-methyl-4-(3-nitrophenyl)-2-phenylquinolin-5(1H,4H,6H)-one (5v):
Yellow solid, mp 236-238 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) 3438, 3077, 2961, 1681, 1576, 1530,
and 1325 cm-1; 1H NMR (300 MHz, CDCl3) δ: 8.35 (1H, s), 8.04 (1H, d, J = 6.6 Hz), 7.82 (1H, d, J = 7.8 Hz), 7.47-
7.36 (6H, m), 5.89 (1H, br s), 4.71 (1H, s), 2.52-2.46 (2H, m), 2.36-2.32 (2H, m), 2.09-1.85 (2H, m), 1.54 (3H, s);
13C NMR (75 MHz, CDCl3) δ: 195.5, 151.6, 148.7, 135.8, 134.8, 130.8, 128.8, 122.7, 121.3, 111.9, 108.4, 43.1,
36.9, 27.9, 21.4, 17.5; Anal. Calcd for C22H20N2O3: C, 73.32; H, 5.59; N, 7.77. Found C, 73.32; H, 5.59; N, 7.77.
N
CH3
O
HH
NO2
7,8-dihydro-3-methyl-4-(3-nitrophenyl)-2,7-diphenylquinolin-5(1H,4H,6H)-one (5w):
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Yellow solid, mp 200-202 °C (CH2Cl2 + EtOAc, equal volumes); IR νmax (KBr) ) 3432, 3071, 2951, 2868, 1681,
1577, 1525, and 1344 cm-1; 1H NMR (300 MHz, CDCl3) δ: 8.15 (1H, d, J = 1.8 Hz), 7.99 (1H, dd, J = 9.9 Hz and J =
0.9 Hz), 7.72 (1H, d, J = 7.5 Hz), 7.45-7.08 (11H, m), 5.86 (1H, br s), 4.66 (1H, s), 3.47-3.42 (1H, m), 2.84-2.48
(4H, m), 1.49 (3H, s); 13C NMR (75 MHz, CDCl3) δ: 194.3, 150.5, 148.7, 148.2, 142.6, 135.7, 134.7, 130.7, 128.9,
128.8, 128.6, 126.9, 126.7, 122.7, 121.3, 112.1, 108.2, 43.4, 39.3, 35.2, 30.9, 17.5; Anal. Calcd for C28H24N2O3: C,
77.04; H, 5.54; N, 6.42. Found C, 77.14; H, 5.54; N, 6.58.
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1H NMR and 13C NMR spectra for 5a-5w
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Preparation of MCM-41 supported HPF6 catalyst
MCM-41 was synthesized according to the literature method1 by the hydrolysis of the structure directing agent
CTAB (cetyltrimethylammonium bromide) and tetraethyl orthosilicate (TEOS), in basic solution with a molar
composition of the reactants 1.0 CTAB:7.5 TEOS:1.8 NaOH:500 H2O. The gelatinous mixture was then
hydrothermally treated at 110 °C for 60 h in a Teflon lined autoclave. After cooling to room temperature the
resultant solid was recovered by filtration, washed with deionized water and dried in air. The collected product was
calcined at 823 K for 8 h to remove the occluded polymeric surfactants. 2.0 g of the as prepared MCM-41 was
dispersed in water (10 mL) in a round bottom flask. 10 mmol of HPF6 was added to the mixture through a constant-
pressure dropping funnel under stirring over a period of 30 min at room temperature. After the addition was
completed, the mixture was stirred for another 24 h at room temperature. The white solid was collected by filtration.
The residue was thoroughly washed with water (10 times) and acetone (5 times). The obtained solid was then dried
in vacuum at 80 °C for 2h and kept in vacuum desiccators. A white precipitate was obtained on treatment of barium
chloride solution with the aqueous extract of the solid after first washing. This precipitate was soluble in excess
hydrochloric acid. This proved the presence of F¯ in the first washing. However no such precipitate was obtained on
same treatment with the aqueous extract of the solid after washing it ten times with distilled water. The aforesaid
observation conclusively proved the absence of F¯ on the solid catalyst after thorough washing with distilled water.
Reference
1 S. Bhunia, R. Sen, S. Koner, Inorganica Chimica Acta, 2010, 363, 3993.
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